1. Field of the Invention
The present invention relates to novel, organic ammonium perhalides which are stable, water soluble and possess high concentrations of easily available oxidizing bromine. More particularly, this invention relates to stable, water soluble organic ammonium perhalides which have utility as water sterilization agents.
2. Description of the Art
Generally, materials which deliver oxidizable bromine have rather low water solubility, as exemplified by elemental bromine, bromine chloride and N-halogenated organics. On the other hand, materials which are water soluble, such as alkali metal bromides, require another powerful oxidizing reagent to effect the release of oxidizable bromine.
The prior art has disclosed compounds of the following Structure I: ##STR2## where R.sub.1 -R.sub.4 are various organic substituents, no more than one of R.sub.1-4 being hydrogen, and X is chlorine, bromine or iodine.
Structure I, where R.sub.1 -R.sub.4 are all hydrogen, is ammonium perhalide: NH.sub.4 XBr.sub.2. D. H. O. John [in "Bromine and its Compounds," edited by Z. E. Jolles, Part II, Chapter 1, page 114, Academic Press, New York, 1966] states that NH.sub.4 Br.sub.3 can be obtained by the electrolysis of a concentrated solution of ammonium bromide. A more direct method of obtaining NH.sub.4 Br.sub.3, mentioned by John, is to dissolve bromine in ammonium bromide solution. The prior art does not show any use or application for this compound.
Structure I where R.sub.4 is hydrogen, R.sub.1 R.sub.2 R.sub.3 NHXBr.sub.2, also known as trisubstituted amine hydrotrihalides, is disclosed by Mercier, et al., Proceedings of the National Academy of Science, U.S., Volume 42, pages 65 to 67 (1956)], who reported that quaternary and ternary alkylammonium chlorides and bromides dissolve readily in bromine with formation of low melting complexes. The authors gave melting points for the following perhalides:
Bu.sub.4 NBr.Br.sub.2 (m 76.degree.), Bu.sub.4 NBr..sub.3 Br.sub.2 (m 37.degree.), Me.sub.3 NHCl.Br.sub.2 (m 37.degree.), Me.sub.3 NHCl.2Br.sub.2 (m 11.5.degree.), Me.sub.3 NHCl.4Br.sub.2 (m 11.5.degree.), Me.sub.3 NHBr.Br.sub.2 (m 34.degree.), Me.sub.3 NHBr.2Br.sub.2 (m 6.degree.), Me.sub.3 NHBr.3Br.sub.2 (m 1.5.degree.) AM.sub.3 NHCl.Br.sub.2 (m 33.degree.).
Also, C. Romers and E. W. M. Keulemans [Proceedings of the Koninklijke Nederlandse Akademie, Volume B61, pages 345-346, 1958] cited (CH.sub.3).sub.3 NHBr.sub.3 as one of the compounds formed when bromine is added to the CCl.sub.4 solution of trimethylamine. The mechanism of its formation is not given, however.
Finally, Structure I, where none of the substituents are hydrogen, R.sub.1 R.sub.2 R.sub.3 R.sub.4 NBrX, yields tetrasubstituted ammonium perhalides. Tetraalkylammonium perhalides are well known to the prior art. Two references detail the preparation of this class of compounds: (1) Frederick D. Chattaway and Geory Hoyle, Journal of Chemical Society, Volume 123, pages 655 to 662, 1923; and (2) Alexander I. Popov and Robert E. Buckles, Inorganic Synthesis, Volume V, pages 176 to 178, McGraw-Hill Book Company, Inc. New York, 1957.
Morton, U.S. Pat. No. 3,152,073 describes the use of tetramethylammonium chlorodibromide for sterilizing water. Morton goes on to disclose a wide variety of tetraalkylammonium polyhalides which contain alkyl groups of six or fewer carbons, suggesting that they may be used as single reagents, directly added to water, to achieve sterilization. It has now been found that, in fact, many of Morton's compounds are not sufficiently soluble in water for use by the method disclosed.
Gannon, et al., United States patent application Ser. No. 048,902, filed Apr. 20, 1987, discloses water sterilization compositions and methods using tetrasubstituted ammonium perhalides as well as trisubstituted amine hydrotribromides. The utility of these compositions and methods have been inhibited by the poor water solubility of the compounds.
Accordingly, a primary objective of this invention is to overcome the disadvantages of the prior art materials.
A further object is to provide a comosition and method of synthesis for novel organosubstituted water-soluble perbromides.
Another is to provide compositions of the character described having utility as biocidal additives in aqueous systems.